CN114425427A - Aromatic hydrocarbon olefin removal catalyst and preparation method and application thereof - Google Patents

Aromatic hydrocarbon olefin removal catalyst and preparation method and application thereof Download PDF

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CN114425427A
CN114425427A CN202011078695.7A CN202011078695A CN114425427A CN 114425427 A CN114425427 A CN 114425427A CN 202011078695 A CN202011078695 A CN 202011078695A CN 114425427 A CN114425427 A CN 114425427A
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catalyst
molecular sieve
mcm
acid
preparation
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CN114425427B (en
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周亚新
王月梅
李为
孔德金
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Sinopec Shanghai Research Institute of Petrochemical Technology
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/80—Mixtures of different zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/084—Y-type faujasite
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    • C07—ORGANIC CHEMISTRY
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
    • C07C7/13—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers by molecular-sieve technique
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
    • C07C7/163—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/44—Hydrogenation of the aromatic hydrocarbons
    • C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
    • C10G45/54—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/37—Acid treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The invention provides a de-olefin catalyst and a preparation method and application thereof, wherein the main component of the de-olefin catalyst comprises a Y/MCM-41 symbiotic molecular sieve, and the ratio of the L acid amount to the B acid amount of the catalyst is (0.2-3) by utilizing the pyridine infrared desorption result at 200 ℃: 1. based on an XRD crystallinity meter, the crystallinity of the fresh catalyst is 100 percent, and the crystallinity of the regenerated catalyst is more than 70 percent. According to the calculation of XRD diffraction peak area, the mass ratio of the Y molecular sieve to the MCM-41 molecular sieve is (1-10): 1. the preparation method comprises the following steps: and carrying out molding roasting, acid treatment and drying on the Y/MCM-41 intergrowth molecular sieve to obtain the aromatic hydrocarbon olefin removal catalyst. The catalyst has the advantages of proper pore structure and surface acidity distribution, high reaction stability and the like.

Description

Aromatic hydrocarbon olefin removal catalyst and preparation method and application thereof
Technical Field
The invention relates to the technical field of catalytic olefin removal, in particular to a catalyst for removing olefin from aromatic hydrocarbon, and a preparation method and application thereof.
Background
Aromatics are a basic feedstock for the petrochemical industry, and are derived primarily from aromatics complexes. The aromatic hydrocarbon products after catalytic reforming reaction all contain a certain amount of olefin impurities. The olefin is active in property, not only is easy to polymerize to form colloid, but also can react with other components to generate non-ideal components, thereby greatly influencing the quality of aromatic hydrocarbon products.
On the other hand, certain petrochemical processes, such as xylene adsorption separation processes, are particularly sensitive to olefins and can be very adversely affected even if the olefin impurities are present in the order of parts per million. In order to obtain qualified chemical raw materials and ensure the smooth proceeding of subsequent processes, refining processes are carried out after reforming, aromatic hydrocarbon extraction, isomerization and toluene disproportionation processes to remove trace olefin impurities.
The argil has an acid center, has certain catalytic polymerization capacity and pore channel adsorption capacity under the conditions of high pressure liquid phase and 150-200 ℃, can enable trace olefin contained in the reformate to undergo reactions such as alkylation, polymerization and the like to generate high-boiling-point compounds, and then is adsorbed by the argil or removed in a subsequent separation process.
The exploitation of clay causes permanent environmental damage. In addition, the deactivated argil containing aromatic hydrocarbon is very harmful to human health, cannot be recycled and can only be treated by landfill, so that serious secondary pollution is caused to the environment. Today, the environmental awareness is continuously strengthened, the problem is more and more concerned by the nation and the people, and the production enterprises urgently need catalytic olefin removal technology capable of solving the problems.
The Ulxon Mobil company developed the Olgone aromatic hydrocarbon refining technology, and adopted the technology without changing the processMCM-22 type molecular sieve catalyst replaces clay to remove trace olefin contained in reformate, and the deactivated catalyst can recover activity by adopting an ex-situ regeneration mode. Molecular sieve type refined catalysts with USY molecular sieves as active centers are developed by Chinese petrochemicals and Chinese sea oil, and DOT-100 and DOT-200 reformed oil non-hydrogenation catalytic olefin removal catalysts are successively developed by China petrochemical Shanghai petrochemical industry research institute. At a weight space velocity of 1.5-1.8h-1Under the conditions of 1.1MPa of reaction pressure and 157-185 ℃ of reaction temperature, the one-way service life of DOT-100 is 7-8 times of that of carclazyte, and the total service life is more than 30 times of that of the carclazyte. The DOT-200 catalyst has the average bromine index of 800mgBr/100g and the weight space velocity of 1.7-1.8h-1Under the condition, the single-cycle life is equal to 15 times of that of the argil, and the total life can reach more than 50 times of that of the argil. The TCDTO-01 reformate catalytic removal system catalyst is developed by the institute of chemical engineering and research of Tianjin in China sea oil, and the catalyst can be regenerated 3-4 times and the total service life of the catalyst reaches 1.5-2 years.
At present, the olefin removing catalyst is more commonly used by Y molecular sieve. The activity of the Y-type molecular sieve is more than 5 times of that of the carclazyte, and the service life is longer. This is because the molecular sieve has small pore passages and the oil-gas diffusion coefficient is generally 10-11cm2Less than s, and a diffusion coefficient of generally 10 in the liquid phase-1cm2On the order of/s, the influence of molecular diffusion during the reaction process is much greater than that of clay.
In the aspect of the pore structure of the molecular sieve, the Y molecular sieve has a super cage, the average effective diameter of the super cage is 1.18nm and is far larger than the diameter of a main pore passage of the super cage by 0.74nm, linear chain macromolecules with smaller molecular diameter can be generated, larger molecules with the diameter of 0.74-1.18nm can be generated, and the abundant and open pore structure ensures the larger pore volume of the molecular sieve, thereby ensuring certain carbon capacity of the molecular sieve and the service life of the molecular sieve catalyst. Because the diameter of the opening of the Y molecular sieve is smaller, macromolecules generated in the olefin alkylation process cannot rapidly escape from the opening of the Y molecular sieve, and are easy to block the opening of the Y molecular sieve to deactivate. In order to enhance macromolecular diffusion, the Y molecular sieve is generally subjected to ultra-stabilization and mesoporous treatment with an acid solution or an alkali solution, so that the effect of improving the carbon capacity of the catalyst is achieved.
Disclosure of Invention
The invention provides an aromatic hydrocarbon olefin-removing catalyst aiming at the problems of weak carbon-containing capacity and short one-way service life of the prior Y molecular sieve olefin-removing catalyst, which has the characteristics of strong carbon-containing capacity and long one-way service life.
The invention aims to provide an arene olefin removal catalyst, which comprises Y/MCM-41 symbiotic molecular sieve, wherein the ratio of the L acid amount to the B acid amount in the catalyst is (0.2-3) by utilizing a pyridine infrared desorption result at 200 ℃:1, preferably (1.3-2): 1.
wherein, the acidity distribution of the catalyst has great influence on the olefin removal reaction performance. The strong acid is excessive, the catalyst is easy to deposit carbon, the inactivation is accelerated, the side reaction degree of the dimethylbenzene is aggravated, and the loss of the dimethylbenzene is increased; if the amount of the strong acid is too small, the removal of aluminum from olefin is not high, the product quality is unqualified, and the subsequent process is influenced. Therefore, the xylene dealkening molecular sieve catalyst should have a suitable range of L acid amount and B acid amount.
The L acid and the B acid in the invention refer to the L acid and the B acid on a molecular sieve informed by a person skilled in the art, wherein the L acid refers to a Lewis acid, and the B acid refers to a Bronsted acid.
In a preferred embodiment, the crystallinity of the fresh catalyst is 100% and the crystallinity of the regenerated catalyst is more than 70%, preferably 70-80% by XRD crystallinity.
The fresh catalyst refers to the catalyst of the invention which is put into use for the first time, and the regenerated catalyst refers to the catalyst which is obtained by using the deactivated catalyst and then regenerating the deactivated catalyst.
The regenerated catalyst refers to a catalyst obtained by regenerating the catalyst of the invention after being deactivated by a regeneration method which is common in the field; the general regeneration method may be to calcine the deactivated catalyst in an air atmosphere, preferably at 500 to 600 ℃ for 1 to 5 hours in an air atmosphere. The regeneration conditions for evaluation of the crystallinity of the catalyst after the catalyst of the present invention is regenerated may be calcination at 500 ℃ for 4 hours in an air atmosphere.
In a preferred embodiment, the mass ratio of the Y molecular sieve to the MCM-41 molecular sieve is (1-10): 1, preferably (2-5): 1.
the second purpose of the present invention is to provide a method for preparing the aromatic dehydrogenation catalyst, which comprises the following steps: and carrying out molding roasting, acid treatment and drying on the Y/MCM-41 intergrowth molecular sieve to obtain the aromatic dehydrogenation catalyst.
In a preferred embodiment, the preparation method comprises the following steps:
step 1, forming and roasting a Y/MCM-41 intergrowth molecular sieve and components including a binder;
step 2, carrying out acid treatment;
and 3, finally drying to obtain the catalyst for olefin removal.
Wherein, the Y/MCM-41 intergrowth molecular sieve can be prepared by the method disclosed by the prior art or can be directly purchased. The forming method in step 2 can adopt the forming method common in the field of catalysts, such as the forming method of mixing the components and extruding into strips, rolling balls or oil columns, and the like.
In a preferred embodiment, in the Y/MCM-41 intergrowth molecular sieve in the step 1, the mass ratio of the Y molecular sieve to the MCM-41 molecular sieve is (1-10): 1, preferably (2-5): 1.
in a preferred embodiment, the temperature of the calcination is 400 to 600 ℃, preferably 500 to 600 ℃.
In a further preferred embodiment, the calcination time is 0.5 to 5 hours, preferably 1 to 3 hours.
In a preferred embodiment, the Y/MCM-41 intergrown molecular sieve is subjected to steam treatment prior to shape calcination.
In a further preferred embodiment, the steam treatment is carried out at 400 to 800 ℃ for 0.5 to 5 hours, preferably 450 to 700 ℃ for 1 to 3 hours.
In a preferred embodiment, the Y/MCM-41 intergrown molecular sieve is silica coated prior to the steam treatment.
In a further preferred embodiment, the Y/MCM-41 intergrown molecular sieve is impregnated in silica sol prior to said steam treatment.
In a preferred embodiment, the silica sol has a mass concentration of 5 to 40%, preferably 5 to 30%.
In a further preferred embodiment, the silica sol is used in an amount of 25 to 2000 parts by weight, preferably 75 to 1000 parts by weight, based on 100 parts by weight of the Y/MCM-41 intergrown molecular sieve.
The Y/MCM-41 intergrowth molecular sieve is pretreated by adopting the silica sol, a layer of amorphous silica is formed on the surface, the excessive damage of a water vapor treatment process to a framework can be prevented, and the silicon can be promoted to migrate into the framework during the ultra-stable dealumination, so that the stability of the framework is improved. Specifically, in the preparation process of the catalyst, the Y/MCM-41 intergrowth molecular sieve is directly treated by water vapor after being dipped and dried in silica sol so as to achieve the purpose of improving the hydrothermal stability of the catalyst. During the steam treatment and the acid treatment, the silica in the impregnated product is partially lost and is therefore low or almost zero in the final catalyst product.
In a preferred embodiment, the acid solution exchange treatment in step 2 is performed at 15-60 ℃, preferably 20-40 ℃ for 2-4 h.
In a preferred embodiment, the acid solution is an aqueous solution of at least one of citric acid, oxalic acid, acetic acid, benzoic acid, hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid, preferably an aqueous solution of at least one of citric acid, hydrochloric acid, and sulfuric acid.
In a further preferred embodiment, the acid solution has a weight concentration of 1 to 10%, preferably 4 to 8%.
In a preferred embodiment, the drying in step 3 is performed at 60 to 200 ℃, preferably 80 to 180 ℃.
The catalyst obtained by the preparation method is characterized in that the ratio of the L acid amount to the B acid amount in the catalyst is (0.2-3) as measured by a pyridine infrared desorption result at 200 ℃:1, preferably (1.3-2): 1.
preferably, the crystallinity of the fresh catalyst is 100 percent and the crystallinity of the regenerated catalyst is more than 70 percent, preferably 70 to 80 percent, measured by XRD crystallinity.
The third object of the present invention is to provide the use of the catalyst of the first object of the present invention or the catalyst for removing olefin from aromatic hydrocarbon obtained by the preparation method of the second object of the present invention in removing olefin from aromatic hydrocarbon, wherein the removing olefin from aromatic hydrocarbon includes removing olefin from xylene and removing olefin from reformate.
So far, no document reports that the Y/MCM-41 intergrowth molecular sieve is used in the reaction of removing olefin from aromatic hydrocarbon. In the reaction, the Y/MCM-41 intergrowth molecular sieve catalyst has better reaction stability and longer service life than the Y molecular sieve catalyst.
In a preferred embodiment, when used for the deolefination of aromatics, comprises: the arene raw material is contacted with the catalyst of the first purpose of the invention or the arene hydrogenation catalyst obtained by the preparation method of the second purpose of the invention to carry out the olefin removal reaction. Wherein, when the arene olefin removal is xylene olefin removal, the raw material mainly comprises C8Mixing aromatic hydrocarbons; when the aromatic hydrocarbon is subjected to olefin removal to obtain reformate olefin removal, the raw material mainly comprises 40-60% of C8Mixing aromatic hydrocarbons, and non-aromatic hydrocarbons, benzene, toluene and C9Aromatic hydrocarbon, C10 +Aromatic hydrocarbons, and the like.
In the invention, the reaction temperature is 140-250 ℃, the reaction pressure is 1.0-3.0 MPa, and the liquid phase mass space velocity is 1h-1-40h-1。
Liquid phase mass space velocity of xylene dealkening on industrial device is 4h-1-10h-1Usually, the liquid phase mass space velocity of the reformate for olefin removal is 1h-1-2h-1. But the catalyst has higher performance, and can improve the liquid phase mass space velocity of the reformate for olefin removal to 3-40h-1. In order to examine the performance of the catalyst in a short time, the method of accelerated deactivation at a high space velocity was used in the examples and comparative examples of the present invention.
Compared with the prior art, the invention has the following beneficial effects:
(1) the catalyst has the advantages of proper surface acidity distribution, strong carbon capacity, long service life and the like;
(2) the characteristic of good reaction stability is obtained by utilizing the characteristics of large pore diameter and pore volume of the MCM-41 molecular sieve.
Detailed Description
While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.
In the examples, the ratio of the amount of L acid to the amount of B acid in the catalyst was determined by pyridine absorption infrared spectroscopy. Taking a certain amount of Y/MCM-41 intergrowth molecular sieve dried at 120 ℃, soaking the molecular sieve in silica sol, filtering, drying again at 120 ℃, and determining the content of the silica and the intergrowth molecular sieve according to weight change.
The Y/MCM-41 intergrowth molecular sieve mainly uses the Y molecular sieve, so that a unimodal method is used for measuring the relative crystallinity of the Y molecular sieve in the catalyst when the crystallinity is calculated. The diffraction intensity of the catalyst is determined by the method of the literature [ study of the change rule of crystallinity of hydrothermal dealuminized USY molecular sieve, petroleum refining and chemical industry, 28(3):16] and the peak height of the diffraction peak of the crystal face of the Y molecular sieve 533 and the full width at half maximum of the peak.
Example 1
Dispersing 5g of NaY molecular sieve with the molecular silica-alumina ratio of 3.6 in 180mL of 1M HCl solution, stirring at normal temperature for 2h, and then putting into a crystallization kettle to react at 100 ℃ for 10h to form gel. Adjusting pH to about 13 with NaOH, slowly dripping 13g of 16 wt% octadecyl trimethyl ammonium chloride solution into the gel, stirring at 50 ℃ for 40min, adjusting pH to about 10 with acetic acid, stirring uniformly, crystallizing in a crystallization kettle at 140 ℃ for 2d, filtering, washing, drying, and roasting at 550 ℃ for 8h to obtain Na-Y/MCM-41. Wherein the content of MCM-41 is 25 percent,
treating Na-Y/MCM-41 at 500 ℃ for 2h, extruding and molding with alumina, drying, and roasting at 600 ℃ for 2 h; and (3) treating the calcined catalyst in a 3% citric acid solution for 2h, and drying to obtain the de-olefin catalyst, wherein the ratio of the L acid amount to the B acid amount is 1.6: 1.
5g of the catalyst is taken to carry out a reformate non-hydrodeolefination test in a fixed bed reactor. The raw material is mixed xylene at the bottom of a reforming deheptanizer, and the bromine index is 1000 mg Br/100g oil. Reaction pressure: 2.0MPa, temperature: 180 ℃, space velocity: at 10.0 time-1The catalyst is deactivated after 240h of reaction by taking the outlet bromine index of 200 mg Br/100g oil as a standard.
Example 2
The procedure of Y/MCM-41 intergrowth molecular sieve synthesis was the same as that of example 1, except that the crystallization conditions were changed to 110 ℃ and the MCM-41 content in the Na-Y/MCM-41 obtained at 3 hours was 18%.
Treating Na-Y/MCM-41 with 680 ℃ water vapor for 1h, extruding and molding with alumina, drying, and roasting at 500 ℃ for 3 h; and (3) treating the calcined catalyst in a 1% hydrochloric acid solution for 4h, and drying to obtain the de-olefin catalyst, wherein the ratio of the L acid amount to the B acid amount is 0.62: 1.
5g of the catalyst is taken to carry out a reformate non-hydrodeolefination test in a fixed bed reactor. The raw material is mixed xylene at the bottom of a reforming deheptanizer, and the bromine index is 1000 mg Br/100g oil. Reaction pressure: 2.0MPa, temperature: 200 ℃, space velocity: at 10.0 time-1The catalyst is deactivated after 220h reaction by taking the outlet bromine index of 200 mg Br/100g oil as a standard.
Example 3
The procedure for the preparation of Na-Y/MCM-41 was the same as in example 1.
Treating Na-Y/MCM-41 at 500 ℃ for 2h, extruding and molding with alumina, drying, and roasting at 600 ℃ for 2 h; and (3) treating the calcined catalyst in a 3% sulfuric acid solution for 2 hours, and drying to obtain the de-olefin catalyst, wherein the ratio of the L acid amount to the B acid amount is 2.8: 1.
5g of the catalyst is taken to carry out a reformate non-hydrodeolefination test in a fixed bed reactor. The raw material is mixed xylene at the bottom of a reforming deheptanizer, and the bromine index is 1000 mg Br/100g oil. Reaction pressure: 2.0MPa, temperature: 180 ℃, space velocity: at 10.0 time-1Taking an outlet bromine index of 200 mg Br/100g oil as a standard, and inactivating the catalyst after 345h of reaction。
Example 4
The procedure for the preparation of Na-Y/MCM-41 was the same as in example 1.
10g of Na-Y/MCM-41 is soaked in 30g of silica sol with the mass fraction of 20% for 2 hours at room temperature, filtered and dried at 100 ℃, and the content of silicon dioxide on the surface of the molecular sieve is 4.3% according to weight change.
Treating the silica sol modified Na-Y/MCM-41 for 2 hours at the temperature of 500 ℃ under the condition of water vapor, extruding and molding the treated silica sol modified Na-Y/MCM-41 with alumina, drying the extruded alumina strip, and roasting the dried alumina strip for 2 hours at the temperature of 600 ℃; and (3) treating the calcined catalyst in a 3% citric acid solution for 2h, and drying to obtain the de-olefin catalyst, wherein the ratio of the L acid amount to the B acid amount is 1.3: 1.
5g of the catalyst is taken to carry out a reformate non-hydrodeolefination test in a fixed bed reactor. The raw material is mixed xylene at the bottom of a reforming deheptanizer, and the bromine index is 1000 mg Br/100g oil. Reaction pressure: 2.0MPa, temperature: 180 ℃, space velocity: at 10.0 time-1The catalyst is deactivated after 270h reaction by taking the outlet bromine index of 200 mg Br/100g oil as a standard.
Example 5
The procedure for the preparation of Na-Y/MCM-41 was the same as in example 2.
10g of Na-Y/MCM-41 is soaked in 35g of silica sol with the mass fraction of 5% for 3 hours at room temperature, filtered and dried at 120 ℃, and the content of silicon dioxide on the surface of the molecular sieve is 1.4% according to weight change.
Treating the silica sol modified Na-Y/MCM-41 for 1h under the condition of water vapor at 680 ℃, extruding and molding the treated silica sol and alumina, drying the extruded alumina, and roasting the extruded alumina for 3h at 500 ℃; and (3) treating the calcined catalyst in a 1% hydrochloric acid solution for 4h, and drying to obtain the de-olefin catalyst, wherein the ratio of the L acid amount to the B acid amount is 0.35: 1.
5g of the catalyst is taken to carry out a reformate non-hydrodeolefination test in a fixed bed reactor. The raw material is mixed xylene at the bottom of a reforming deheptanizer, and the bromine index is 1000 mg Br/100g oil. Reaction pressure: 2.0MPa, temperature: 200 ℃, space velocity: at 10.0 time-1The catalyst was deactivated after 235h reaction, using an outlet bromine index of 200 mg Br/100g oil as standard.
Comparative example 1
Using the NaY molecular sieve of example 1, steam treatment, shape calcination and acid treatment under the same conditions as in example 1 were carried out to obtain a Y molecular sieve catalyst.
5g of the catalyst is taken to carry out a reformate non-hydrodeolefination test in a fixed bed reactor. The raw material is mixed xylene at the bottom of a reforming deheptanizer, and the bromine index is 1000 mg Br/100g oil. Reaction pressure: 2.0MPa, temperature: 180 ℃, space velocity: at 10.0 time-1The catalyst is deactivated after reaction for 150h by taking the outlet bromine index of 200 mg Br/100g oil as a standard.
Comparative example 2
The Na-Y/MCM-41 intergrowth molecular sieve was prepared according to the same method as in example 1.
Treating Na-Y/MCM-41 for 2h under the condition of 500 ℃ water vapor, cooling and taking out, treating for 2h in 3% citric acid solution, drying, extruding and molding with alumina, drying, and roasting at 600 ℃ for 2h to obtain the de-olefin catalyst, wherein the ratio of the L acid amount to the B acid amount is 0.7: 1.
5g of the catalyst is taken to carry out a reformate non-hydrodeolefination test in a fixed bed reactor. The raw material is mixed xylene at the bottom of a reforming deheptanizer, and the bromine index is 1000 mg Br/100g oil. Reaction pressure: 2.0MPa, temperature: 180 ℃, space velocity: at 10.0 time-1The catalyst was deactivated after 175h of reaction, based on an outlet bromine index of 200 mg Br/100g oil.

Claims (12)

1. The catalyst comprises a Y/MCM-41 symbiotic molecular sieve, and the ratio of the L acid amount to the B acid amount in the catalyst is (0.2-3) by utilizing a pyridine infrared desorption result at 200 ℃: 1.
2. the catalyst of claim 1 wherein the fresh catalyst crystallinity is 100% and the regenerated catalyst crystallinity is greater than 70% by XRD crystallinity.
3. The catalyst according to claim 1, wherein the mass ratio of the Y molecular sieve to the MCM-41 molecular sieve is (1-10): 1.
4. the catalyst according to claim 1 to 3,
the ratio of the L acid amount to the B acid amount in the catalyst is (1.3-2) by using the pyridine infrared desorption result at 200 ℃: 1; and/or
The mass ratio of the Y molecular sieve to the MCM-41 molecular sieve is (2-5): 1.
5. a method for preparing the aromatic hydrocarbon dealkening catalyst according to any one of claims 1 to 4, comprising: and carrying out molding roasting, acid treatment and drying on the Y/MCM-41 intergrowth molecular sieve to obtain the aromatic dehydrogenation catalyst.
6. The method of manufacturing according to claim 5, comprising the steps of:
step 1, forming and roasting a Y/MCM-41 intergrowth molecular sieve and components including a binder;
step 2, carrying out acid treatment;
and 3, finally drying to obtain the catalyst for olefin removal.
7. The preparation method according to claim 6, wherein in the Y/MCM-41 intergrowth molecular sieve in the step 1, the mass ratio of the Y molecular sieve to the MCM-41 molecular sieve is (1-10): 1, preferably (2-5): 1.
8. the production method according to claim 5,
the roasting temperature in the step 1 is 400-600 ℃, and preferably 500-600 ℃; and/or
The acid treatment in the step 2 is carried out for 2-4 h at 15-60 ℃, preferably 20-40 ℃; and/or
And 3, drying at 60-200 ℃, preferably 80-180 ℃.
9. The preparation method according to any one of claims 5 to 8, wherein the Y/MCM-41 intergrowth molecular sieve is subjected to steam treatment before molding and roasting, and preferably, the steam treatment is performed at 400 to 800 ℃ for 0.5 to 5 hours.
10. The preparation method according to claim 9, wherein the Y/MCM-41 intergrown molecular sieve is subjected to a silica coating treatment before the steam treatment, preferably, the Y/MCM-41 intergrown molecular sieve is impregnated in silica sol.
11. The method according to claim 10,
the mass concentration of the silica sol is 5-40%, preferably 5-30%; and/or
The amount of the silica sol is 25 to 2000 parts by weight, preferably 75 to 1000 parts by weight, based on 100 parts by weight of the Y/MCM-41 intergrowth molecular sieve.
12. Use of the aromatic hydrocarbon dealkenation catalyst according to any one of claims 1 to 4 or the aromatic hydrocarbon dealkenation catalyst obtained by the preparation method according to any one of claims 5 to 11 in the dealkenation of aromatic hydrocarbons.
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CN103878015A (en) * 2013-09-30 2014-06-25 洛阳市科创石化科技开发有限公司 Molecular sieve catalyst for MTP (methanol to propylene) as well as preparation method thereof
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WO2001030942A1 (en) * 1999-10-28 2001-05-03 Mobil Oil Corporation Process for btx purification
CN102069008A (en) * 2009-11-19 2011-05-25 中国石油化工股份有限公司 Catalyst for removing olefin in reformed arene and preparation method thereof
CN102000599A (en) * 2010-11-09 2011-04-06 中国海洋石油总公司 Preparation method of catalyst for deeply desorbing trace olefins in aromatic hydrocarbon
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